Azo-dyestuffs



Patented June23,

will

' AZO-DYESTUFFS meal-mi seux mewuneim BubenBascl. switzerland. asclgnorsto SocietyotOhemicaI Industry in Basie, Basel, Swltaerland lVoDrawing 'AAccording to this invention valuable'dyestuiis are obtained byintroducing into any aao-b'ody at least one v i 5 \Rr-O-BI group,wherein R1 stands for hydrogen, alkyl, or aralkyl or acidyl, R2 for analiphatic hydrocarbon radical consisting of at least two carbon atoms..

and R3 for 'alkyl or aralkyL- Here and throughout the specificationalkyl not only means the homologues oi the CH3- and Callsgroups, but

also the substituted radicals thereof such as Cal-14C], C2H4N(CH:|)2,OaHiSOiH,

and so forth. 'The term alkyl comprises also radicals with double bonds,such as, for example,

causing a diazo-compound of an aromatic base to react with a couplingcomponent which contains at least one alkyloxy aikylamino-group,aralkyloxyalkylamino-group or. alkyleneoxyalkylamino-group. Another formof the process;

I consists in substituting-in anaminoazo-dyestui! the primary orsecondary amino-group by subse- 'quent treatment with an alkyletherwhichv still. contains at least one group capable oi reacting with theprimary or secondary amino-group oi the dyestuff. a

This may be done, for example, by causing the dyestufl' which contains aprimary or secondary 1 amino-group to react with anaryl-sulfonic acidester or sultonic acid ester oi a polyhydric alcohol with 2 or-moreC-atoms containing at least one etherifled OH-group, such asno-cm-onr-o-cm, no-cm-cm-crn-o-cm,

o-cn,, n HO--CH:C HO-CHr-CHs-CHeJl-Cflg,

OH] I n! in which formulas another alkyl-group, such as, for example,the Cam-group, 0!? a group containing still more carbonatoms, may alsoreplace the CHa-gtoup linked to the 'O-atOm Furth r contain the group.as aminoazotoluene,

pplication June 8, 1933, Serial No. In Switzerland July 9, 1933 1'1 (c1.zoo-as) stance. a -NI-I-CH=CH:'-Br-group or a --N'I-I--CHz,CH:-CH'a-Brgroup, treated with an alcoholate. v

The dyestuffs thus obtained have the general may be ywherein A and Bstand for nuclei of the benzene or naphthalene series, and R1, R2 .andR3 have the meanings already indicated above, These dyestuflsformyellow, orange, brown, red, violet blue or black powders, and dissolvein solvents,

such as water (ii the dyestufis contain sulfonic groups capable offorming alkali salts), or acetic the MM radical. The process consist. inester or. glacial acetic acid or, pyridine (ii'the dyecotton, artificialsilk from regenerated cellulose.

cellulose esters and cellulose others and artificial silk consisting'oisuch materialain the shades ina 'be obtained by combining anydiazotizing components with such coupling components which a Rr-0R|wherein R1, R: and B: have the meaning already indicated'above. In thiscase there may be used as 'diazotizing components aniline, toluidine,nitraniline, particularly para-nitraniline, chloraniline or a sulionicor carboxylic acid oiany or these, for instance sulianilic acid,metanilic acid or the like, nitrochloroaniline, particularly 2- chloro-anitraniline, 2,6-dichloro 4 nitraniline, anisidine, nitroanisidines andchloroanisidines, particularly d-nitro-ortho-anlsidine: dinitroanilines;particularly 2,4-dinitraniline, dinitrochloroanilines, particularly2,4-dinitro-6-chloraniline; ortho-aminophenol or its homologues andanalogues, such as ortho-aminocresols, nitroaminophenols, particularly5-nitro-ortho-aminophenol, chloro-aminophenols and their sulionic acids,'naphthylamines, naphthylamine sulionlc acids, such, as1,8-aminonaphthol sulionic acid, 1,8-

aminonaphthol-mii -disulionic acid, or the toluene-sullonic acid estersthereof; aminoazoben acne and its homologues and analogues, suchaminoazobenzene-sulfonic acids, aminoam-dyestuiis, such as the azo-dye-ONE-CHz-CHr-O-CHI N(p-ethoxyethyl) -aniline, N methyl-N(fl-methoxyethyl)-aniline or N-methyl-N(p-ethoxyethyl) -aniline, the formulas of the lasttwo being I./GHa

and

CHr-CH:-C: l

respectively, N-ethyl-N(p-methoxyethyl) -aniline or 'N ethylN(,9-ethoxyethyl) aniline, N (-13- -methoxyethyl) -3-methyl-aniline ofthe formula QNH-CHg-AJIh-O-CH:

or N(p ethoxyethyl) 3 methyl aniline, N03- methoxyethyll-Z-methoxy 5methyl-aniline oi the formula NH-CHi-CHz-O-CH:

, Hz or Nip-ethoxyethyb -2-methoxy 5 methyl-aniline, N(p methoxyethyl)-2,5-dimethoxy-aniline o! the formula NH-OHFCHz-O-CH:

-CHa I I or N(fi-ethoxyethyl) -2,5-dimethoxy-aniline, N- ethylms-methoxyethyl) -2-methoxy-5-methylanaline or the iormula N/C:H|

cm-cHPo-cm H I r ,5; Nqs -.ethoxyethyl) 2 methoxy-5- methyl ine,N-ethyl-N(p-methoxyethyl) -2,5- ethcrty aniline of the formulaCHr-CHr-OC I or N-etl'l'yl-N(p-ethoxyethyl) -2,5-dimethoxy-aniline, orN(di-p-methoxyethyl) -aniline oi the for- 1(armour-04:11; v \CHPCHPOOHUor N(p-methoxyethyl-l-aminonaphthalene of the formula or N(p-methoxyethyl) -2-aminonaphthalene, further derivatives ofdiaminobenzenes, suchas, for

example, the compound of the iormula produced f0r-example by alkylatingm-nitraniline and subsequent reduction, or derivatives 01 aminophenols,such as, for example, the compound of the formula which may be obtainedby diazotizing the aqueous solution or the corresponding amino-compoundand replacing the diazo-group by an OH-group by heating.

The arylaminoalkylethers may be made, for example by condensing, thecorresponding amine, for instance aniline, ethyl-aniline, 1-amino-2-methoxy-5-methylbenzene or the like with an ether of a polyhydricalcohol which contains at.

least one non-etherified hydroxyl-group, or by treatment with a sulfuricacid ester or dialkyl v ether sulfate or aryl-sulfonic acid ester of oneof these (if necessary in the presence of an agent that binds acid, suchas sodium carbonate, magnesia, chalk or the like), for instance with theparatoluenesulionic acid ester of glycol-monomethylether'orglycol-mono-ethylether, such as is obtained, for instance, by treatingglycolmono-methyl-ether or glycol-mono-ethylether with para-toluenesulfonic chloride. They can also be made by condensing a halogen-etherwith the amine or by etherifying the corresponding aryl-amino-alcohol,or by causing an aryl-aminohalogenalkyl-compound to react withanalcoholate, or by causing an aryl-compound which contains in the nucleusa substituent capable of reacting to react with an aminoalkylether, forinstance a halogen in' ortho-position to a nitrogroup. I

The dyestufl's of the above general formula may also be obtained it thediazotizing component contains the characteristic \R: O-R| group whereinR1, R: and Rs have the meaning already indicated above. Such methods ofpro-. ducing these dyestufls are described further below and areillustrated by examples.

As already mentioned these dyestufis may be used for dyeing textiles ofvarious kinds. They can of course also be used for other purposes, forexample as pigments, for dyeing lacquers and varnishes, for dyeingpaper, and so forth. They can also be used as intermediate products forthe production of further azo-dyestufls, and if required for theproduction of further dyestuffgroups.

The non-sultonated dyestuilfs are in particular used for dyeing estersand ethers of cellulose, and when brought into suitable iorm orsuspended in a suitable medium, have a pronounced afllnity for celluloseesters and ethers, particularly' acetate silk, which they dye very fasttints.

The non-sulfonated dyestuffs may be brought into a finely subdividedform for example by grinding them with a dispersing agent, such as thesulfonated residue-from the manufacture of benzaldehyde, a turpentineoil or the like, in

the presence of water to produce a fine paste, or they may be convertedin presence of further quantities of the aforesaid'or other auxiliarysubstances, for example sulflte cellulose waste liquor, by cautiouslydrying them. preferably in avacuum, at a temperature not too high, intodry pulverlzable preparations.

The following. may further dyeing acetate-sllk:-- 7

Yellow to orange red tints are obtained by coupling aniline orpara-nitraniline with N(pmethoxyethyl) -aniline or N(p-ethoxyethyl)-aniline; red to Bordeaux-red tints by coupling parabe mentioned fornitraniline, i-n itro-ortho-anisidine or 2-chlorod-nitranilinewithN-ethyl-NKp-methoxyethyl)- aniline; red violet tints to violet browntints by coupling 5-nitro-ortho-aminophenol or 2,4-dinitraniline or4,6-dinitro-ortho-anisidine withN(s-methonyethyl)-2-methoxy-5-methyl-aniline wherein R1, R2 and Rs havethe already indicated meanings, such as, for example, the d-ainino-d'[N-ethyl-Nr (p methoxycthynl aminoaao benzone of the, formula or theei-amlno-d'-N(di fi-methoxyethyl) amino azmbenzene, or the t-amino-ilN-(w-hydroxyethyl) N(,6-methoxyethyl) l-aminoazo benzene, arediazotized, and cotton, which itself has been prepared in known mannerwith arylides of 2,3- hydroxynaphthoic-acid, 2,3hydfroxyanthracenecarboxylic acid, hydroxycarbazole-carbonylic acid or hydroxybenao-carbazole-carboxylic acid, is introduced into the diam-solution thusobtained.- the same is dyed fast black shades. in these dyestuffswherein the characteristic Rr0- t group, R1, R3 and Rs having themeanings already indicated above, is present in the diazotizingcomponent, and which correspond for exple to the formula CHr-CHs-O-CHtthe symbols A and Bof the above general formula are, also benzenenuclei.

The sulfonated dyestufis are used for dyeing wool, silk and cotton. Theconstitution of the dyestuffs is also here decisive for theirapplication. Thus the coupling componentsmentioned on page 2 yield with'sulfanilic acid yellow dyestuf fs,'with nitroanilinesulfonic acidorange to red'dyestufis which may be suitable for dyeing wool or silk.Diazotizing components, such as dehydrothiotoluidine-sulfonic acid, leadto dyestuffs suitable for dyeing cotton.

Compounds, such as -amino-l-[N-ethyl-N-(,B-rnethoxyethyl)lamino-benzene, obtained by treating theN-ethyl-N-(p-methoxyethyl) -aniline with nitric acid and subsequentreduction yield blue wool-dyestuffs when diazotized and coupled v withpen-derivatives of the naphthalene, such as 1,8-dihydroxynaphthalene or1,8-arninonaphtholsulfonie acids; If care has been taken, by furthersuitable substitution in thebenzene nucleus,

that an energetic diazotizing component is obtained, for example byintroducing halogen or SOz-aryl groups, blue dyestuffs may also be ob.tained with N-acidyl derivatives of the Lil-aminonaphthol-suifonicacids. The peri-derivatives of the naphthalene which come into questionhere are the 1,8 dihydroxynaphthalene i sulfonic' acid, the 1,8dihydroxynaphthalene 3,6 -dlsulfonlc acid, the1,8-aminonaphthol-4-sulfonic acid, or the 3,6=- or 4,6- or2,4-disulfcnic acids,

and the N-acetyl, N-chloracetyl, N-benzoyl and N-para-toluene sulfonicderivatives thereof.

Blue dyestuifs are also obtained by treating with saponifying agentsdyestuffs, such as the coupling products of thel,8-dihydroxynaphthaiene-l-sulfonic acid or the 3,6-disulfonlc acid,with N-acidyl-derivatives of the 4-diazo-1-N-(fimethoxyethyDf aminobenzene. As acyl group there comes into consideration here for example Ithe acetyl-group. Similarly behaves the NO- group. In all thesedyestufis containing a naphthalene residue, for example in the dyestufi'of the formula HO OH CHr-O CHPCHK the benzene nucleus corresponds to thesymbol B and the naphthalene nucleus corresponds to the symbol A of thegeneral formula:

wherein the symbols A, B, R1, R2 and R3 have the meanings alreadyexplained above. This gen-.

eral formula does not only correspond to monoazo-dyestuffs, but thenuclei A and B may also c as substituents arylN=N--groups so that theformulaappliesalso to disazo and polyazodyestuffs.

Such products may be obtained by choosing as a coupling componentcontaining the group wherein R1, R2 and R3 have the meanings .al-

- ready indicated above, such a component which is capable of couplingtwice (for example a metaphenylene-diamineor an aminonaphtholderivative). The coupling components containing the oup m-o-n.

wherein R1, R: and Re have the meanings already indicated above, mayalso be combined with such diazo compounds which already contain one orseveral azo-groups. This will for mstance be the case when producingcotton dye-.

stuifs which may, for example, possess thefollowing constitution:- a

CHg-CHr-O-CH;

OH NH! In such a dyestuii. the benzene nucleus 1 corresponds to thesymbol B and the benzene nucleus 2 to the symbol A. If the N/Bl group,wherein R1, R2 and B: have the meanin s already indicated above, isbound to. a naphthalene nucleus, an aromatic nucleus of the naphthaleneseries corresponds to the symbol B. If the coupling components mentionedon page 2 are coupled with diazotizing components, such asdiazotizedl-naphthylamine-4-sulionic acid or the diazotizd azo-dyestufi,which itself is obtained from diazotized 1-naphthylamlne-6- sulfonicacid (1 mol.) and l-naphthylamine-6- sulfonic acid (1 mol.) the symbol Aor the symbols Aand 3 correspond to aromatic nuclei of the naphthaleneseries. Such dyestu'fi's are also cited farther back in Example 'I oftion.

The following examples illustrate the invention, the parts being byweight:

Example 1 13.8 parts of finely pulverized para-nitraniline are stirredwith 300 parts of water and the susobtained of the formula is filteredand washed. It is a red powder which, after it has been brought into afine state of subthis specificadivision by adding agents havingdispersing properties, dyes acetate silk lustrous red tints. TheN-ethyl-N(p methoxyethyl) aniline may be made, torexample, as follows:

To a mixture of 121 parts of mono-ethylaniline "with 58 parts ofcalcined sodium carbonate there are added, by drops, in the course of 3m4 hours and at a temperature of about -130 C., while intensivelystirring, 230 parts of the p-toluene sulfonic acid ester ofglycol-mono-methylether of the formula (obtainable in known manner byreaction of glycol-mono-methylether with para-toluene-sulfochloride andaqueous caustic soda solution) The reaction occurs with intenseevolution of carbon dioxide and separation of sodium toluenesulfonate.Stirring is continued for some hours at about C. and, after cooling, thewhole is stirred with water; the oil thus separated is withdrawn fromthe aqueous portion in a separating funnel and then distilled in avacuum. After a first running of mono-ethylaniline there distilsN-ethyl-N(p-methoxyethyl) -aniline of the formucnronro-om in the form ofa water-clear oil of agreeable aromatic odor and of boiling point 93 C.under 2 mm. pressure.

Example 2 from 16.8 parts of nitro-anisidine (mrxocmmopnzm is mixed with13.6 parts of crystallized sodium acetate and then added to a solutionof 17.9 parts of N-ethyl -N(fl-methoxyethyl) -aniline in dilutehydrochloric acid. The dyestuff thus obtained of the formula CzHs No C IcHr-cm-o-om is a dark red powder which dyes acetate sill: dark redtints. Example 3 17.25 parts of 2-chloro-4-nitraniline are ground withwater and diazotized by means of 25 parts or concentrated hydrochloricacid and '7 parts of sodium nitrite. The diazo-solution thus obtained ismixed with 13.6 parts of crystallized sodium acetate and allowed to flowinto a solution of 17.9 parts of N-ethy1-N(,8-methoxyethyl) -aniline indilute hydrochloric acid. The dyestufl. of the formula separates in theform of a red violet powder. It dyes acetate silk Bordeaux red tints.

Example 4 Into a solution of parts of N-(p-methoxyethyl)-2-methoxy5-methyl-aniline in dilute hydrochloric acid there is allowed to flow adiazosolution prepared in known manner from 183 The diazo-solution madein the usual manner I 'Y parts of dinitraniline. When coupling has been75 completed by the addition of sodium acetate the dyestufl of theformula N| N= Qua-carcinoma.

I H: i

v 7 NO: which has separated, is filtered. It is a dark violet powder,soluble in ethyl acetate to a violet solution and capable of dyeingacetate silk violet tints, which can be discharged to a pure white.

The N -(p methoxyethyl) 2 methoxy 5 methyl-aniline of the formula o-cniNH-OHg-OHrO-CE Ha v Emaybe made, for instance, by adding in drops, inthe course of 3 to 4 hours, 230 grams of the ptoluene sulfonic acidester of glycol monomethylether to a'mixture of 137 parts of l-amino-2-methoxy-5-methyl-benzene with 58 parts of calcined sodium carbonate atabout 120 C. The mass is stirred for some hours at this mmperature andworked up as described in Example 1; the

desired ether is thus obtained in the form of a bright oil which boilsat108 C. to 110 C. under s mm. pressure.

A- dyestufi dyeing acetate silk blue tints is obtained by coupling thediazotized. 6-chloro-2:4- dinitraniline with the N-(p ethoxyethyl) 1aminonaphthalene. The dyestufl corresponds with the formula and forms ablack powder which dissolves in acetic ester to a blue solution. Thesame coupling component combined with diazotized 1,8-

OuNa When dry and Y dark blue powder which dissolves in water to a bluesolution and dyes wool in an acid bath blue tints.

pulverized this dyestufi forms a Examp 5 19.5 parts ofsodium-sulfanilate are dissolved in 200 parts of water and the solutionis diazotized by meansoi 7 parts of sodium nitrite and 25 partsofconcentrated hydrochloric acid: The diazosolution is mixed with asolution of 17.9 parts of N ethyl-N(,s-methoxyethyl) -aniline., Thedyestufl thusobtained of theformula N g O 0 \CHrcHr0 cm aikyl-group andR: for an alkyl-group, which dyes wool in an acid bath yellow tints. Itcan also be used forproducin i printing eiiects on acetate silk.

I Emmpled Cotton yarn is impregnated for hour at 20-25 C. with asolution containing per liter 8 grams of 2,3-hydroxynaphthoicacid-iP-methomanilide, 12 ccm. of caustic soda solution of 34 B., 7 com.of Turkey red oil, and 7 com. oi! formaldehyde solution of 40 per centstrength. The yam is well wrung out and then developed in a solution'neutralized with sodium acetate containing per liter 2 grams ofdiazotized 4-amino-3-chloro-6- methoxy l'-[N ethyl N -(pmethowethyl)lamino-azobenz'ene of the formula I a P Hr-0-4Jm CaHt The goods are thenrinsed and scoped. There are obtained very pure deep black tints ofexcellent fastness properties. v The dyestuif may also be produced insub- 7 stance. It forms a black powder which dissolves in pyridine toablackish solution.

What'weclaimiszv l. Azo-dyestufi's of the general idrmula I l R1A-\N=N-BN/ I wherein A and B stand for nuclei of the benuen ornaphthalene series, R1 'for hydrogen or an alkyl-group, R2 for analiphatic hydrocarbon radical consisting of at least two carbon atoms,and Rs for an alkyl-group, which products form yellow, orange, brown,red, violet, blue or black powders, dissolve in solvents to yellow,orange, brown, red, violet, blue orblack solutions, and dye textilessimilar shades.

2. Azo-dyestufis of the general formula wherein A and B stand for nucleiof the or naphthalene series, B; for hydrogen or y up, and R3 for analkyl-group, w products form yellow, orange, brown, violet, blue orblack powders, dissolve in. solvents to yellow, orange, brown, red,violet, blue or solutions, and dye textiles similar wherein A d B standfor nuclei 1. m zene or naphthalene series, R1 i'or hydrogen or analkyl-group, and Rs for an alkyl-group, whi products form yellow,orange, br, red, mm or blue powders, dissolve in solvents to ow. orange,brown, violet 'or blue solutions, .1 dye textiles similar shades.

a. Unsuli'onated monoazo-d'yestufla of new eral formula 7 products formyellow, orange, brown, red, violet or blue powders, dissolve in aceticester to yellow, orange,- brown, red, violet or blue solutions, and dyeacetate artificial silk similar shades.

5. Unsulfonated monoazo-dyestufis oi the general formula A-N=N-B-NCHg-CH:O-Ri

wherein A stands for a benzene nucleus and B for a nucleus of thebenzene or naphthalene series, R1 for hydrogen or an alkyl group and R3for an alkyl-group, which products form yellow, orange, brown, red,violet or blue powders, dissolve in acetic ester to yellow, orange,brown,

red, violet or blue solutions, and dye acetate artificial silk similarshades.

6. Unsulfonated monoazo-dyestuil's of the general formula.

Rx AN=N-BN/ wherein A stands-fora benzene nucleus carrying anitro-g'roup in p-position to the N=N- group, B for a nucleus of thebenzene or naphthalene series, R1- for hydrogen or an alkylgroup, and R3for an alkyl-group, which products form orange, brown, red, violet orblue powders, dissolve in acetic ester to orange, brown, red, violet orblue solutions, and dye acetate artificial silk similar shades.

7. Unsulfonated monoazo-dyestufl's o! the general formula wherein A andB stand for nuclei of the benzene series, the nucleus A carrying a.nitro-group in p-position to the -N=N-group, and R: stands for analkyl-group, which products form orange, brown, red or violet powders,dissolve in acetic ester to orange, brown, red. or violet solutions, anddye acetate artificial silk similar 8. Non-sultonated monoaao-dyestuflsor the' general tormula which product forms a scarlet-red powder,dissolves in acetic ester to a scarlet-red solution and dyes acetateartificial silk, fast scarlet shades.

10. The non-suli'onated monoazo-dyestufi of the formula r onr-om-o-cmwhich product forms a red powder, dissolves in acetic ester to ablue-red solution and dyes acetate artificial silk pure blue-red-violetshades.

11. The non-sulfonated monoazo-dyestufl of the formula o-om N N=N aNam-crn-o-cm N0: Ha

which product forms a dark violet powder, dissolves in acetic ester to aviolet solution and dyes acetate artificial silk violet shades.

FRIEDRICH FELIX. WILHELM HUBER.

